EP1574561A1 - Parfümierte Waschmitteltablette - Google Patents

Parfümierte Waschmitteltablette Download PDF

Info

Publication number
EP1574561A1
EP1574561A1 EP04447060A EP04447060A EP1574561A1 EP 1574561 A1 EP1574561 A1 EP 1574561A1 EP 04447060 A EP04447060 A EP 04447060A EP 04447060 A EP04447060 A EP 04447060A EP 1574561 A1 EP1574561 A1 EP 1574561A1
Authority
EP
European Patent Office
Prior art keywords
perfume
detergent tablet
tablet according
region
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP04447060A
Other languages
English (en)
French (fr)
Inventor
Maria Leonor Grandio Portabales
Jose Maria Velazquez
Jean Wevers (Nmn)
Michael Green (NMN)
Miguel Estrella de Castro (NMN)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP04447060A priority Critical patent/EP1574561A1/de
Priority to JP2007502117A priority patent/JP2007525590A/ja
Priority to CA002558206A priority patent/CA2558206A1/en
Priority to BRPI0508538-1A priority patent/BRPI0508538A/pt
Priority to PCT/US2005/007966 priority patent/WO2005087906A1/en
Priority to US11/078,102 priority patent/US20050202992A1/en
Publication of EP1574561A1 publication Critical patent/EP1574561A1/de
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to detergent tablets having improved perfume stability and delivering a longer-lasting dry fabric odour benefit.
  • compositions in form of tablets become increasingly popular with consumers as they offer simple dosing, easy storage and handling.
  • tablet compositions have many benefits such as reduced transportation costs, handling costs and storage costs. Tablets are typically formed by compression of the various components. The tablets produced must be sufficiently robust to be able to withstand handling and transportation without sustaining damage. In addition, the tablets must also dissolve quickly so that the detergent components are released into the wash water as soon as possible at the beginning of the wash cycle. Such performance aspects are an important feature of the detergent tablets, and although they are not necessarily the focus of the present invention, they are inherently a part of the background of the present invention.
  • the present invention relates to detergent tablet that provides lasting perfume benefits to fabrics that have been laundered with this product. Moreover, this composition minimizes the losses of perfume during both production process, storage over time and laundering.
  • zeolite X and Y a faujasite-type zeolite loaded with perfume.
  • zeolite X and Y a faujasite-type zeolite loaded with perfume.
  • East German Patent Publication No. 137,599, published Sep. 12, 1979 teaches compositions for use in powdered washing agents to provide thermoregulated release of perfume. Zeolites A, X and Y are taught for use in these compositions.
  • compositions which comprise zeolites having pore size of at least 6 Angstroms, perfume releaseably incorporated in the pores of the zeolite, and a matrix coated on the perfumed zeolite, the matrix comprising a water-soluble composition comprising from 0%-80% by weight of at least one solid polyol containing more than 3 hydroxyl moieties and from 20%-100% by weight of a fluid diol or polyol, in which the perfume is substantially insoluble and in which the solid polyol is substantially soluble.
  • WO 97/34982 discloses particles comprising perfume loaded zeolite and a release barrier, which is an agent derived from a wax and having a size larger than the size of the pore openings of the zeolite carrier.
  • WO01/40430 a particle comprising a core of a porous carrier material containing an additive, such as a perfume, in its pores; a first coating of a hydrophobic oil encapsulating said core, and a second coating of a water-soluble but oil-insoluble material, such as starch or modified starch, encapsulating the hydrophobic-oil coated core.
  • WO02/090481 provides for a temperature and humidity stable unit dose perfume delivery article that comprises a perfume composition, a material selected from a perfume carrier, preferably zeolite, a hydrating material and mixtures thereof, and a humidity resistant package, wherein at least 30% by volume of the components are in the form of fine powders or particulates having a mean particle size of less than 100 microns.
  • WO02/089862 describes an air freshening composition that includes porous carrier particles having a perfume composition entrapped therein, a second component for retarding the absorption and/or adsorption of water and/or for providing moisture to the porous carrier particles, and optionally, a third component selected from free perfume, colorant, disintegrant, water swelling agent and/or porosity modifier.
  • An objective of the present invention is to provide detergent tablets which have sufficient hardness to survive handling and transportation, will rapidly dissolve in the wash water without leaving residue, and will release perfume components onto the fabric not only during the washing cycle but as well during and after the drying stage, while ensuring the stability of the detergent tablet from its preparation to the end use.
  • an objective of the present invention is to ensure the long-term stability of the perfume components of detergent tablets.
  • the present invention provides for improved retention of the perfume in the zeolite carrier material such that more perfume is retained on fabric through the laundering process to be released from the dry fabric in the presence of atmospheric moisture or humidity.
  • the present invention also provides the benefit of continued odour release from laundered fabrics when exposed humidity while being stored, dried or ironed, providing an enduring fragrance.
  • the present invention relates to a detergent tablet comprising from 0.05% to 10%, preferably from 0.1% to 5%, more preferably from 0.1% to 3% by weight of the total detergent tablet of a perfume particle comprising a core of a porous material comprising a perfume in its pores; wherein the perfume particle is comprised at a greater concentration in one region of the tablet (region 2) than in another region thereof (region 1).
  • the articles of the present invention have sufficient hardness to survive handling and transportation, will rapidly dissolve in water during a short cycle washing and/or rinsing process without leaving residue, and will deposit perfume components onto the fabric and provide for a slow release of those components when exposed to atmospheric moisture. It is believed that excellent long-term stability of perfume particles is insured by separating the perfume particle into a discrete region of the detergent tablet.
  • the porous carrier material is typically selected from zeolites, macroporous zeolites, amorphous silicates, crystalline nonlayer silicates, layer silicates, silica, calcium carbonates, calcium/sodium carbonate double salts, sodium carbonates, clays, sodalites, alkali metal phosphates, chitin microbeads, carboxyalkylcelluloses, carboxyalkylstarches, cyclodextrins, porous starches, and mixtures thereof.
  • the carrier material is a zeolite such as Zeolite X, Zeolite Y, and mixtures thereof.
  • Particularly preferred porous carriers are zeolite particles with a nominal pore size of at least about 6 Angstroms to effectively incorporate perfume into their pores.
  • these zeolites provide a channel or cage-like structure in which the perfume molecules are trapped.
  • such perfumed zeolites are not sufficiently storage-stable for commercial use in tablet detergents, particularly due to premature release of perfume upon moisture absorption.
  • the perfume-loaded zeolite can be stabilised when formulated into a separated discrete region of the tablet detergent.
  • the formulation of the perfume particle into a discrete region of the tablet provides a physical separation from the remaining of the detergent composition and a further barrier to moisture uptake and therefore provides an improved stability of the perfume loaded zeolite.
  • the perfume substantially remains within the pores of the zeolite particles.
  • the perfume particle is a perfume-loaded zeolite (PLZ).
  • the perfume particle of the present invention have a hygroscopicity value of less than 80%.
  • the "hygroscopicity value”, as used herein, means the level of moisture uptake by the particles, as measured by the percent increase in weight of the particles under the following test method.
  • the hygroscopicity value required for the present invention particles is determined by placing 2 grams of particles in an open container petri dish under conditions of 90°F and 80% relative humidity for a period of 4 weeks. The percent increase in weight of the particles at the end of this time is the particles' hygroscopicity value as used herein.
  • Preferred particles of the present invention have a hygroscopicity value of less than 50%, more preferably less than 30%.
  • the perfume particle typically comprises from 1% to 60% of perfume, preferably from 1% to 30%, more preferably from 10% to 20% by weight of perfume particle; and from 40% to 99% of the carrier, preferably from 70% to 99%, more preferably from 80% to 90% by weight of the perfume particle.
  • the perfume particle comprises a porous carrier material and a perfume loaded into said carrier material. It will be encompassed in the detergent tablet of the present invention at a level of from 0.05% to 10%, preferably from 0.1% to 5%, more preferably from 0.1% to 3% by weight of the total detergent tablet.
  • Such ingredients may be mixed in a number of different ways.
  • basic equipment used for this purpose can vary from a 10-20g coffee grinder to a 100-500g food processor or even a 200-1000g kitchen mixer.
  • Procedure consists of placing the carrier material particles (zeolite) in the equipment and pouring the laundry additive at the same time that mixing occurs. Mixing time is from 0.5 to 15 minutes.
  • the loaded carrier material (zeolite) is then allowed to rest for a period from 0.5 to 48 hours before further processing. During the loading process when heating occurs, cool jacketing may be used as an option.
  • suitable equipment is a mixer of the Littleford type, which is a batch type mixer with plows and chopper blades that operate at high RPM's, to continuously mix the powder or mixture of powders while liquid perfume oil is being sprayed thereon.
  • the porous carrier material means any material capable of supporting (e.g., by adsorption into the pores) the perfume of the present invention.
  • Such materials include porous solids such as zeolites.
  • Preferred zeolites are selected from zeolite X, zeolite Y and mixtures thereof.
  • zeolite used herein refers to a crystalline aluminosilicate material.
  • the structural formula of a zeolite is based on the crystal unit cell, the smallest unit of structure represented by Mm/n[(AlO2)m(SiO2)y].xH20 where n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100. Most preferably, y/m is 1 to 5.
  • the cation M can be Group IA and Group IIA elements, such as sodium, potassium, magnesium, and calcium.
  • a zeolite useful herein is a faujasite-type zeolite, including Type X Zeolite or Type Y Zeolite, both with a pore size typically in the range of from 4 to 10 Angstrom units, preferably 8 Angstrom units.
  • aluminosilicate zeolite materials useful for this invention are commercially available. Methods for producing X and Y-type zeolites are well- known and available in standard texts. Preferred synthetic crystalline aluminosilicate materials useful herein are available under the designation Type X or Type Y.
  • the crystalline aluminosilicate material is Type X and is selected from the following:
  • the crystalline aluminosilicate material is Type Y and is selected from the following:
  • the class of zeolites known as, "Zeolite MAP" may also be employed in the present invention.
  • Zeolites are described in on pages 5 to 8 of WO95/27030 (published on October 12, 1995 by the Procter & Gamble Company).
  • Zeolites used in the present invention are in particle form having an average particle size from 0.5 microns to 120 microns, preferably from 0.5 microns to 30 microns, as measured by standard particle size analysis technique.
  • the size of the zeolite particles allows them to be entrained in the fabrics with which they come in contact. Once established on the fabric surface, the zeolites can begin to release their incorporated laundry agents, especially when subjected to heat or humid conditions.
  • perfume is used to indicate any odoriferous material which is subsequently released into the aqueous bath and/or onto fabrics or other surfaces contacted therewith.
  • the perfume will most often be liquid at ambient temperatures.
  • a wide variety of chemicals are known for perfume uses, including materials such as aldehydes, especially C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof, ketones, alcohols and esters. More commonly, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfumes.
  • the perfumes herein can be relatively simple in their compositions or can comprise highly sophisticated complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.
  • Typical perfumes can comprise, for example, woody/earthy bases containing exotic materials such as sandalwood, civet and patchouli oil.
  • the perfumes can be of a light floral fragrance, e.g., rose extract, violet extract, and lilac.
  • the perfumes can also be formulated to provide desirable fruity odors, e.g., lime, lemon, and orange. Any chemically compatible material which exudes a pleasant or otherwise desirable odor can be used in the perfumed compositions herein.
  • preferred perfumes are those which have the ability to be incorporated into the pores of the carrier, and hence their utility as components for delivery from the carrier through an aqueous environment.
  • WO 98/41607 describes on page 9, line 16 to page 11, line 1, the characteristic physical parameters of perfume molecules which affect their ability to be incorporated into the pores of a carrier, such as a zeolite: the longest and widest measures, the cross sectional area, the molecular volume molecular area and the shape.
  • compositions whereby perfume agents are being delivered by the compositions sensory perception is also required for a benefit to be seen by the consumer.
  • perfume delivery particles the preferred perfume agents have a threshold of noticeability (measured as odor detection thresholds ("ODT”) under carefully controlled GC conditions as described in detail hereinafter) less than or equal to 50 parts per billion (“ppb”).
  • ODT odor detection thresholds
  • ppb parts per billion
  • Agents with ODTs above 50 ppb up to 1 part per million (“ppm”) are less preferred.
  • Agents with ODTs above 1 ppm are preferably avoided.
  • Laundry agent perfume mixtures useful for the present invention perfume delivery particles preferably comprise from 0% to 80% of deliverable agents with ODTs above 50 ppb up to 1ppm, and from 20% to 100% (preferably from 30% to 100%; more preferably from 50% to 100%) of deliverable agents with ODTs less than or equal to 50 ppb.
  • perfumes carried through the laundry process and thereafter released into the air around the dried fabrics e.g., such as the space around the fabric during storage. This requires movement of the perfume out of the zeolite pores with subsequent partitioning into the air around the fabric.
  • Preferred perfume agents are therefore further identified on the basis of their volatility. Boiling point is used herein as a measure of volatility and preferred materials have a boiling point less than 300°C.
  • Laundry agent perfume mixtures useful for the present invention preferably comprise at least 50% of deliverable agents with boiling point less than 300°C (preferably at least 60%; more preferably at least 70%).
  • preferred perfume delivery particles herein for use in laundry detergents comprise compositions wherein at least 80%, and more preferably at least 90%, of the deliverable perfume agents have a weighted average ClogP value ranging from 1.0 to 16, and more preferably from 2.0 to 8. Most preferably, the deliverable perfume agents or mixtures have a weighted average ClogP value between 3 and 4. While not wishing to be bound by theory, it is believed that perfume materials having the preferred ClogP values are sufficiently hydrophobic to be held inside the pores of the zeolite carrier and deposited onto fabrics during the wash, yet are able to be released from the zeolite pores at a reasonable rate from dry fabric to provide a noticeable benefit. ClogP values are obtained as follows.
  • perfume ingredients are characterized by their octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of most perfume ingredients are large, they are more conveniently given in the form of their logarithm to the base 10, logP.
  • the logP of many perfume ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), contains many, along with citations to the original literature.
  • logP logP
  • ClogP The "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990).
  • the fragment approach is based on the chemical structure of each perfume ingredient and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • the ClogP values which are the most reliable and widely used estimates for this physicochemical property, can be used instead of the experimental logP values in the selection of perfume ingredients.
  • the gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution.
  • the air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.2 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material.
  • solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed. The average over all panelists determines the threshold of noticeability.
  • Particularly preferred perfumes for use in the present invention are those perfumes referred to as high impact perfumes and characterized by having: (1) a standard B.P. of 300°C or lower at 760 mm Hg, and; (2) a ClogP, or an experimental logP, of 2 or higher, and; (3) an ODT of less than or equal to 50ppb.
  • the Type X or Type Y Zeolites to be used as the preferred carrier herein preferably contain less than 15% desorbable water, more preferably less than 8% desorbable water, and most preferably less than 5% desorbable water.
  • Such materials may be obtained by first activating/dehydrating by heating to 150-350°C, optionally with reduced pressure (from 0.001-20 Torr). After activation, the agent is slowly and thoroughly mixed with the activated zeolite and, optionally, heated to 60°C or up to 2 hours to accelerate absorption equilibrium within the zeolite particles. The perfume/zeolite mixture is then cooled to room temperature and is in the form of a free-flowing powder.
  • the present perfume particles have typically a particle size of from 3 to 100 microns as measured by standard particle size analysis technique.
  • perfume particles perfume loaded on Zeolite X
  • storage conditions 27°C and 60% Relative Humidity (RH), or 35°C and 80% RH
  • Particles are homogenized and dosed according to regional real washing conditions. They are mixed with odorless base granule, previously approved for this kind of test.
  • Perfume intensity scores for the particles are registered in terms of Dry Fabric Odor. Particles with perfume loaded zeolite are able to provide more than 5 points of advantage, in a perfume intensity scale, compared against a similarly aged control with sprayed on perfume alone after 5 to 7 days drying.
  • the perfume particle of the present invention can further be coated and/or encapsulated.
  • perfume-loaded zeolite particles in the form of a free-flowing powder are thoroughly coated with a hydrophobic oil such as mineral oil or perfume oil.
  • a hydrophobic oil such as mineral oil or perfume oil.
  • the hydrophobic-oil coated particles are mixed to a solution of modified starch (CAPSUL TM , National Starch & Chemicals) and agitated to form an emulsion.
  • the emulsion is then spray-dried using a spray dryer having a spraying system such as co-current with a spinning disk, with vaneless disk, with vaned disk or wheel or with two-fluid mist spray nozzle.
  • Typical conditions involve an inlet temperature of from 120°C to 220°C and an outlet temperature of from 50°C to 220°C.
  • WO01/40430 describes a first coating of a hydrophobic oil and a second coating of a water-soluble but oil-insoluble material, such as starch or modified starch, encapsulating the hydrophobic-oil coated core.
  • a water-soluble but oil-insoluble material such as starch or modified starch
  • Such intermediate oil coating material can be a perfume oil which can be the same as or different from the perfume loaded into the carrier, or a non-perfume oil, such as mineral oil; preferably with a weighted average ClogP lower than the weighted average ClogP of the perfume loaded in the pores of the carrier.
  • the external encapsulating material (p13, line 18 to page 15, line 14) is derived from one or more at least partially water soluble or dispersible compounds in an aqueous wash environment and are preferably selected from the following classes of materials: Carbohydrates; All natural or synthetic gums; Chitin and chitosan; Cellulose and cellulose derivatives; Water soluble polymers; Waxes; Plasticizers; Long Chain (C10-C35) fatty compounds; and/or Natural proteins.
  • Laundry and cleaning additives or agents can be further included in the perfume particle of the present invention and can be the same as or different from those agents which are typically used to formulate the remainder of the detergent tablets of the present invention.
  • the detergent tablet of the present invention will comprise at least 2 different regions.
  • the perfume particle is comprised at a greater concentration in one region of the tablet (region 2) than in another region thereof (region 1).
  • region 1 is the compacted matrix of the detergent tablet and is usually referred to as the core;
  • region 2 is a discrete region that will be in the form of a single or a plurality of coating, insert, dimple, beads, particles...
  • all perfume particles will be comprised in region 2 of the detergent tablet.
  • the different regions can either have the same or different colors.
  • Multi-layer tablets having 2 or 3 layers are preferred.
  • Single- and multi-layer tablets having exacavations and/or cavities and/or holes in all sorts of geometrical forms are also included in the present invention.
  • Particularly preferred are tablets in which embedded geometrical shapes such as hemispheres protrude from the surface of the tablet.
  • the detergent tablet herein comprise two regions, the first region in the form of a shaped body having at least one mold therein and the second region is in the form of a compressed or shaped body contained, for example by physical or chemical adhesion, within the mold of the first region. More preferably, the perfume particle is comprised within the mold.
  • the detergent tablet comprises as region 2, a plurality of particles.
  • Such discrete particles comprise the perfume particle as this causes the perfume to be more evenly distributed around the wash thus helping to ensure a more uniform application of the perfume to the fabrics as well as an improved stability of the perfume particle.
  • the discrete particles comprising the perfume particles have a average particle size of from 0.5mm to 10mm, more preferably from 1.5mm to 5mm, even more preferably from 2mm to 4mm.
  • the discrete particles can be in any 3-dimensional shape such as in the form of granules, beads, noodles, pellets, compressed tablets, filled sachets, and mixtures thereof.
  • the particles are in the form of beads. It is preferred that the discrete particles are substantially spherical in shape.
  • the discrete region comprising the perfume particle can comprise in addition to the perfume particle, further ingredients such as fabric softening agent, a binder, a dissolution aid, a builder, an alkalinity source, a dye, a free perfume and/or an effervescent system (as described below in more details).
  • further ingredients such as fabric softening agent, a binder, a dissolution aid, a builder, an alkalinity source, a dye, a free perfume and/or an effervescent system (as described below in more details).
  • such particles When formulated as discrete particles, such particles should preferably be strong enough to withstand the compression step of the tablet making process.
  • the resistance to compression can be controlled or improved by adding certain ingredients, such as dissolution aids, silicas, or porous carriers such as Zeolite X or Y.
  • Binders can also be selected to reduce the deformability of the region can be selected from (i) Polymeric materials include polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000, polyethylene glycols with an average molecular weight of from 600 to 10,000, Copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid; (ii) Sugars, sugar acids, sugar alcohols, and preferably sorbitol. The binder may optionally be blended with one or more additional compounds such as viscosity modifiers or structuring agents such as lewis acids, preferably boric acid.
  • the detergent tablet of the present invention can be formulated for use in any cleaning process such as dishwashing and laundry, preferably for use in a fabric washing process.
  • the detergent tablet can comprise a wide variety of different ingredients, such as building agents, effervescent system, enzymes, dissolution aids, disintegrants, bleaching agents, suds supressors, surfactants (nonionic, anionic, cationic, amphoteric, and/or zwitterionic), fabric softening agents, alkalinity sources, colorants, perfumes, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, anti-redeposition agents, soil release polymers, hydrotropes, fluorescents, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, optical brighteners, and combinations thereof.
  • building agents such as building agents, effervescent system, enzymes, dissolution aids, disintegrants, bleaching agents, suds supressors, surfactants (nonionic, anionic, cationic, amphoteric, and/or zwitterionic), fabric softening agents, alkalinity
  • compositions suitable for use in a laundry machine washing method typically contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Laundry compositions can also contain softening agents, as additional detergent components.
  • compositions herein can also be used as detergent additive products.
  • Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process.
  • the detergent tablets of the present invention are made by tabletting a detergent base powder.
  • the base powder is typically a pre-formed detergent granule.
  • the pre-formed detergent granule may be an agglomerated particle or in any other form.
  • the average particle size of the base powder is typically from 100 ⁇ m to 2,000 ⁇ m, preferably from 200 ⁇ m, or from 300 ⁇ m, or from 400 ⁇ m, or from 500 ⁇ m and preferably to 1,800 ⁇ m, or to 1,500 ⁇ m, or to 1,200 ⁇ m, or to 1,000 ⁇ m, or to 800 ⁇ m, or to 700 ⁇ m. Most preferably, the average particle size of the base powder is from 400 ⁇ m to 700 ⁇ m.
  • the bulk density of the base powder is typically from 400 g/l to 1,200 g/l, preferably from 500 g/l to 950 g/l, more preferably from 600 g/l to 900 g/l, and most preferably from 650 g/l to 850 g/l.
  • the detergent tablet can further comprise a free perfume, i.e. other than the perfume particle of the present invention.
  • the free perfume can be the same as or different from the perfume oil loaded into the carrier.
  • the free perfume will provide the detergent tablet odour, most of the damp fabric odor and a small amount of dry fabric odour.
  • the perfume particle with provide the long lasting dry fabric odour. Since, the free perfume and loaded perfume will give different perfume benefits, it is preferred that the free perfume and loaded perfume are of different compositions.
  • the detergent tablets of the present invention typically comprise a free perfume at a level of 0.05% to 2%, preferably 0.1% to 1% by weight of the total detergent tablet.
  • the free perfume may be blended into the tablet composition (such as by spray-on techniques) along with the perfume-containing particle.
  • the free perfume is formulated within the region 2 together with the perfume particle.
  • the base powder when formulated in a laundry detergent tablet, preferably comprises a builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the base powder.
  • Highly preferred builder compounds for use in the present invention are water-soluble phosphate builders.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21, and salts of phytic acid.
  • Examples of partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na z [(AlO 2 ) z (SiO 2 )y] ⁇ H 2 O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the base powder herein preferably comprises at least one surfactant, preferably two or more surfactants.
  • the total surfactant concentration is typically from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the base powder.
  • Suitable surfactants are selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • detergent active compounds are available and are fully described in WO 02/31100 published on April 18, 2002 and assigned to P&G and in the literature, e.g., in "Surface-active agents and detergents", Vol. I and II, by Schwartz, Perry and Berch.
  • the detergent tablets herein comprise a disintegration aid, such as:
  • the detergent tablets of the present invention can be dosed to the laundry machine via the drawer or directly into the drum, potentially via a dispending device, such as a net.
  • Tablets can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry, in the food industry, or in the detergent industry.
  • the detergent tablets can be made in any size or shape and can, if desired, be coated.
  • the particulate materials used for making the tablet can be made by any particulation or granulation process.
  • An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600 kg/m 3 or lower.
  • Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g.
  • Lödige TM CB and/or Lödige TM KM mixers include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
  • Individual particles can also be any other particle, granule, sphere or grain.
  • the particulate materials may be mixed together by any conventional means. Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s).
  • a binder preferably a non-gelling binder; can be sprayed on to the mix of some, or, on the mix of all of the particulate materials, either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed.
  • a finely divided flow aid dustting agent such as zeolites, carbonates, silicas
  • the tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting.
  • Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy TM , Korch TM , Manesty TM , or Bonals TM).
  • Tablets prepared should preferably have a diameter of between 40mm and 60mm, and a weight between 25 and 100 g.
  • the ratio of height to diameter (or width) of the tablets is preferably greater than 1:3, more preferably greater than 1:2.
  • the compaction pressure used for preparing these tablets need not exceed 5000 kN/m, preferably not exceed 3000 kN/m, and most preferably not exceed 1000 kN/m.
  • the detergent tablet typically has a diameter of between 20 mm and 60 mm, and typically having a weight of from 10 g to 100 g.
  • the ratio of tablet height to tablet width is typically greater than 1:3.
  • the tablet typically has a density of at least 900 g/l, preferably at least 950 g/l, and preferably less than 2,000 g/l, more preferably less than 1,500 g/l, most preferably less than 1,200 g/l.
  • the discrete particle comprising the perfume particle are preferably manufactured in an extrusion process.
  • the equipment typically used for this invention is a Twin Screw Extruder (TSE), and a Marumerizer® or Spheronizer.
  • TSE Twin Screw Extruder
  • a blend of different powder ingredients comprising the perfume particle is fed into the TSE.
  • a free perfume can be added, typically at a level of from 2% to 16%, preferably 6% to 12%, more preferably from 8% to 10% of the final discrete particle.
  • a binder is then incorporated, so that extrudates are formed. These extrudates are cutted and rounded up in a spheronization process, such as in a Marumerizer ® (ex. Fuji Paudal).
  • the detergent tablet of the present invention will be packaged into a humidity resistant package. It has been found that the long term stability of the perfume components and the perfume delivery profile of the detergent tablet will be further improved by packaging the tablets with materials that provide a moisture barrier, expressed as a moisture vapor transmission rate (MVTR), of at less than 1g H 2 0/day/m 2 , preferably less than 0.1g H 2 0/day/m 2 , and more preferably less than 0.02g H 2 0/day/m 2 .
  • MVTR moisture vapor transmission rate
  • the stability of the perfumed detergent tablets and its ability to effective release the perfume components is further improved when such materials be protected from atmospheric moisture with a package having specific moisture barrier characteristics. Hydration of powder components is detrimental to the perfumed tablet because deactivation prolongs the dissolution time and may leave residues in the washing machine and/or on fabrics. Further, if there is incomplete dissolution, the perfume carrier material will not be completely released to deposit on the fabric surface such that the benefit delivered will only be a fraction of the target benefit. In addition, where the perfume is entrapped in a moisture sensitive carrier such as zeolite, the perfume will be desorbed upon adsorption of water, especially water vapour. Water vapour can effectively displace about 95-98% of the perfume entrapped inside the zeolite cavity.
  • the choice of packaging material for the perfumed detergent tablet of the present invention can be determined by following several steps. First determine the critical amount of water that can be adsorbed or absorbed by the perfumed detergent tablet without losing performance, where the loss of performance can be quantified by the level of perfume components in the headspace above or on the dried fabrics, by the incomplete dissolution of the composition/article, etc. Water absorption may be determined by exposing the composition/article to constant humidity and determining the mass gained over time. Then, evaluate the performance (analytical and/or sensory) of each perfumed detergent tablet to determine the critical quantity of water. Second, determine the surface area of the package in which the perfumed tablets will be packaged and sold in the trade.
  • Tabulated values of MVTR provided in technical references generally report data determined at 28-38°C, and 80%-90% relative humidity such that they represent worse case scenario ambient conditions. Selecting the packaging material under these conditions will ensure long term stability of the article.
  • the article is packaged so that moisture penetration must occur through a continuous layer, and the moisture vapour transmission rate of the layer is less than 1g H 2 O/m 2 /day, Preferably less than 0.5g H 2 O/m 2 /day, more preferably less than 0.1g H 2 O/m 2 /day, even more preferably less than 0.02 g H 2 O/m 2 /day and still more preferably 0g H 2 O/m 2 /day, to ensure article stability.
  • the packaging selected to ensure minimal perfume oil loss from the zeolite must meet several requirements. Films that are permeable to water vapor will not be sufficient to ensure stability. Determination of effective packaging materials must be done on a case-by-case basis since perfume materials will have various odor detection thresholds, and performance benefits that may be detected even after about 20-40% of the oil is lost from the zeolite.
  • fragrances are normally composed of volatile compositions, so that a low MVTR prevents not only the ingress of water, but egress of perfume.
  • Materials suitable for this use include monolayer, co-extruded or laminated films.
  • the packaging system is composed of vapour metallised bi-oriented polypropylene with an MVTR of less than 1 g/day/m2.
  • the film may have various thicknesses. The thickness should typically be between 10 and 150 ⁇ m, preferably between 15 and 120 ⁇ m, more preferably between 20 and 100 ⁇ m, more preferably between 20 and 80 ⁇ m and most preferably between 20 and 30 ⁇ m.
  • the packaging system comprises at least a micro-hole. There may also be more than 1 micro-hole. These can be made using a pin.
  • An advantage of using a micro-hole in combination of a material having the claimed MVTR is that the problem of ingress of moisture and the problem of evacuation of gas can be decoupled. Indeed the ingress of moisture is readily controlled by choosing the right MVTR, whereas a micro-hole has only a negligible influence on ingress of moisture because it is present only at some points on the packaging system without modifying the characteristics of the remaining surface of the packaging system and a microhole will not have influence enough if there is no pressure gradient. As a pressure gradient will appear precisely when gas needs to be evacuated to prevent deformation of the packaging system the micro-hole will fulfil its function without significant influence on the ingress of moisture.
  • the tablets of the invention can be wrapped after being deposed onto the packaging system.
  • a cold seal or an adhesive is particularly suited to the packaging system of the present invention. Indeed a band of cold seal or a band of adhesive may be applied to the surface of the packaging system at a position adjacent to the second end of the packaging system, so that this band may provide the initial seal of the packaging system. In such a case the cold seal band may correspond to a region having a cohesive surface, i.e., a surface which will adhere only to another cohesive surface.
  • the method of washing fabrics and depositing perfume thereto comprises contacting said fabrics with an aqueous wash liquor comprising at least 100ppm of conventional detersive ingredients, including at least 0. 1ppm of the perfume particle.
  • the conventional detersive ingredient can be added separately or formulated within the detergent tablet of the present invention.
  • the detergent tablet works under all circumstances, but is particularly useful for providing odor benefits during the laundering process and on wet and dry fabrics.
  • the method comprises contacting fabrics with an aqueous liquor comprising the conventional detersive ingredients and the perfume particle, such that the perfumed particles are entrained on the fabrics, storing line-dried fabrics under ambient conditions with humidity of at least 20%, drying the fabric in a conventional automatic dryer, or applying heat to fabrics which have been line-dried or machine dried by conventional ironing means (preferably with steam or pre-wetting).
  • Example 1 Entrapping Perfume on Porous Carrier Particles
  • An amount of 170 g of perfume is added at a rate of about 5 g/sec through a perfume nozzle (80 psi, average droplet size of 90 micrometres) to 830 g of Zeolite 13 X (ex. UOP Limited - Molsiv Absorbents) under high agitation in single batch Loedige Plow mixer.
  • a cooling jacket at 20°C is used to remove the heat generated during perfume entrapment (aprox. 280 kJ/kg perfume).
  • the perfume loaded in the zeolite has the following composition: Material name % Violiff 2.5 Frutene 15.0 Methyl Iso Butenyl Tetrahydro Pyran 7.5 Cymal 10.0 Florhydral 15.0 Delta damascone 15.0 Ionone Beta 25.0 P.T. Bucinal 10.0
  • Example 2 Perfume particles in discrete particles (region 2)
  • compositions according to Table 1 are mixed during 5 minutes in a Loedige mixer. This mix is fed into a Twin Screw Extruder (TSE ZSK 25 ex. Werner & Pfleiderer) at a level of approx. 74% by weight and then optionally, mixed with approx. 8% of a perfume oil and kneaded with the binder system described below (approx.15 %) into a dough, which is transported to the end of the TSE and pressed through a 2 mm die plate producing extrudates.
  • TSE ZSK 25 ex. Werner & Pfleiderer twin Screw Extruder
  • the binder system used in the above extrusion process comprises 95%wt PEG 4000 and 5%wt PEG 200.
  • the two components are mixed during 2 minutes using a Jankel & Kunkel mixer (KW 20 DZM), and then added to the TSE binder feeder.
  • the final discrete particles have the compositions described in Table 2 below:
  • Example 3 Perfume particles in discrete particles (region 2)
  • Example 4 Detergent tablet composition
  • the detergent composition of the core was prepared by admixing the granular components in a mixing drum for 5 minutes to create a homogenous particle mixture. During this mixing, the spray-on's were carried out with a nozzle and hot air using a binder.
  • the discrete particles have been manufactured as in example 2 and have the compositions described in examples 2 and 3 above.
  • the multi-phase tablet composition was prepared using an Instron 4400 testing machine and a standard die for manual tablet manufacturing. 35g of the detergent core was fed into the dye of 41x41 mm with rounded edges that has a ratio of 2.5 mm. The mix was compressed with a force of 1,500 N with a punch that has a suitable shape to form a concave mold of 25 mm diameter and 10 mm depth in the tablet. The shaped punch was carefully removed leaving the tablet into the dye. 2.3 g of discrete particles that form the second region were introduced into the mold left in the tablet shape and a final compression of 1,700 N was applied to manufacture the multiphase tablet using a flat normal punch. The tablet is then manually ejected from the dye.
  • the detergent tablets of example 4 above (40g each), can be coated by dipping the tablet into a mixture of 95 g adipic acid with 5 g calcium polystyrene sulphonate resin (ex. Purolite), at a temperature of 160 °C.
  • the uncoated tablets of example 4 or the coated tablets of example 5 can be packaged in a flow-wrap of 20 micron vapour metallised (Aluminium) BiOriented Polypropylene film with cold glue pattern.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Packages (AREA)
  • Wrappers (AREA)
  • Fats And Perfumes (AREA)
EP04447060A 2004-03-11 2004-03-11 Parfümierte Waschmitteltablette Ceased EP1574561A1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP04447060A EP1574561A1 (de) 2004-03-11 2004-03-11 Parfümierte Waschmitteltablette
JP2007502117A JP2007525590A (ja) 2004-03-11 2005-03-10 香料を有する洗剤の錠剤
CA002558206A CA2558206A1 (en) 2004-03-11 2005-03-10 Perfumed detergent tablets
BRPI0508538-1A BRPI0508538A (pt) 2004-03-11 2005-03-10 tabletes detergentes perfumados
PCT/US2005/007966 WO2005087906A1 (en) 2004-03-11 2005-03-10 Perfumed detergent tablets
US11/078,102 US20050202992A1 (en) 2004-03-11 2005-03-11 Perfumed detergent tablets

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP04447060A EP1574561A1 (de) 2004-03-11 2004-03-11 Parfümierte Waschmitteltablette

Publications (1)

Publication Number Publication Date
EP1574561A1 true EP1574561A1 (de) 2005-09-14

Family

ID=34814478

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04447060A Ceased EP1574561A1 (de) 2004-03-11 2004-03-11 Parfümierte Waschmitteltablette

Country Status (6)

Country Link
US (1) US20050202992A1 (de)
EP (1) EP1574561A1 (de)
JP (1) JP2007525590A (de)
BR (1) BRPI0508538A (de)
CA (1) CA2558206A1 (de)
WO (1) WO2005087906A1 (de)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199887A (zh) * 2015-10-19 2015-12-30 茗燕生物科技(上海)有限公司 速溶型柚皮提取物洗衣片及其制作方法
WO2017069933A1 (en) * 2015-10-19 2017-04-27 The Procter & Gamble Company Process for associating a scent with a laundry article
EP2355776B1 (de) * 2008-12-08 2017-11-15 The Procter and Gamble Company Poröses und lösliches feststoffsubstrat sowie oberflächenhaftende anorganische partikelparfumkomplexe
US11525104B2 (en) 2019-11-20 2022-12-13 The Procter & Gamble Company Porous dissolvable solid structure
US11529292B2 (en) 2017-01-27 2022-12-20 The Procter & Gamble Company Compositions in the form of dissolvable solid structures
US11597191B2 (en) 2019-10-14 2023-03-07 The Procter & Gamble Company Biodegradable and/or home compostable sachet containing a solid article
US11666514B2 (en) 2018-09-21 2023-06-06 The Procter & Gamble Company Fibrous structures containing polymer matrix particles with perfume ingredients
US11679066B2 (en) 2019-06-28 2023-06-20 The Procter & Gamble Company Dissolvable solid fibrous articles containing anionic surfactants
US11826439B2 (en) 2020-09-10 2023-11-28 The Procter & Gamble Company Dissolvable solid article containing anti-bacterial actives
US11925698B2 (en) 2020-07-31 2024-03-12 The Procter & Gamble Company Water-soluble fibrous pouch containing prills for hair care
US11944693B2 (en) 2010-07-02 2024-04-02 The Procter & Gamble Company Method for delivering an active agent
US11944696B2 (en) 2010-07-02 2024-04-02 The Procter & Gamble Company Detergent product and method for making same
US11951194B2 (en) 2017-01-27 2024-04-09 The Procter & Gamble Company Compositions in the form of dissolvable solid structures comprising effervescent agglomerated particles
US11970789B2 (en) 2010-07-02 2024-04-30 The Procter & Gamble Company Filaments comprising an active agent nonwoven webs and methods for making same
US12029799B2 (en) 2022-04-27 2024-07-09 The Procter & Gamble Company Conditioning hair care compositions in the form of dissolvable solid structures

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4657671B2 (ja) * 2004-10-14 2011-03-23 花王株式会社 香料粒子
JP2009500515A (ja) * 2005-07-11 2009-01-08 ジェネンコー・インターナショナル・インク 消費者用布処理用酵素タブレットとその製法
US20080032907A1 (en) * 2006-08-01 2008-02-07 Bernard Patenaude Shaver head cleanser
EP2101829A2 (de) * 2006-10-13 2009-09-23 The Procter and Gamble Company Spender für reinigungsmitteldosierungen mit duftkomponente
US8765170B2 (en) 2008-01-30 2014-07-01 The Procter & Gamble Company Personal care composition in the form of an article
US8188022B2 (en) * 2008-04-11 2012-05-29 Amcol International Corporation Multilayer fragrance encapsulation comprising kappa carrageenan
MX337657B (es) 2008-04-16 2016-03-14 Procter & Gamble Composicion no espumante para el cuidado personal en forma de un articulo.
WO2010077628A2 (en) * 2008-12-08 2010-07-08 The Procter & Gamble Company Personal care composition in the form of an atricle having a porous, dissolvable solid structure
EP2355783B1 (de) 2008-12-08 2016-10-12 The Procter and Gamble Company Verfahren zur herstellung eines sich nach gebrauch auflösenden artikels zur zuführung von tensiden
MX2011005727A (es) 2008-12-08 2011-06-21 Procter & Gamble Composicion de cuidado personal en la forma de un articulo que tiene una estructura solida soluble porosa.
WO2011071969A1 (en) * 2009-12-08 2011-06-16 The Procter & Gamble Company A porous, dissolvable solid substrate and a cationic surfactant conditioner material
MX339322B (es) 2009-12-08 2016-05-20 Procter & Gamble Un sustrato solido, soluble y poroso y recubrimiento fijo de superficie que comprende microesferas de matriz.
MX2012006247A (es) 2009-12-08 2012-06-19 Procter & Gamble Un sustrato solido soluble poroso y un recubrimiento fijo de superficie de acondicionador de surfactante cationico.
US9173826B2 (en) 2010-02-16 2015-11-03 The Procter & Gamble Company Porous, dissolvable solid substrate and surface resident coating comprising a zync pyrithione
GB201003892D0 (en) * 2010-03-09 2010-04-21 Reckitt Benckiser Nv Detergent composition
WO2012003349A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Dissolvable fibrous web structure article comprising active agents
US20180163325A1 (en) 2016-12-09 2018-06-14 Robert Wayne Glenn, Jr. Dissolvable fibrous web structure article comprising active agents
MX336047B (es) 2011-05-27 2016-01-07 Procter & Gamble Articulo colorante solido soluble para el pelo.
US8439981B2 (en) 2011-05-27 2013-05-14 The Procter & Gamble Company Soluble solid hair coloring article
US8444716B1 (en) 2012-05-23 2013-05-21 The Procter & Gamble Company Soluble solid hair coloring article
US9233055B2 (en) 2012-10-12 2016-01-12 The Procter & Gamble Company Personal care composition in the form of a dissolvable article
JP2015044771A (ja) * 2013-08-29 2015-03-12 不易糊工業株式会社 香料含有樹脂組成物及びその製造方法
JP6362226B2 (ja) 2014-04-22 2018-07-25 ザ プロクター アンド ギャンブル カンパニー 溶解性固体構造物の形態の組成物
US20180303725A1 (en) * 2017-04-21 2018-10-25 Robert Nathan Alder Customizable dissolvable objects and related methods of manufacture
CN110650723A (zh) 2017-05-16 2020-01-03 宝洁公司 可溶性固体结构形式的调理毛发护理组合物
JP1629688S (de) 2018-07-16 2019-04-15
MX2021015391A (es) 2019-07-03 2022-01-24 Procter & Gamble Estructuras fibrosas que contienen surfactantes cationicos y acidos solubles.
USD939359S1 (en) 2019-10-01 2021-12-28 The Procter And Gamble Plaza Packaging for a single dose personal care product
EP4065068A1 (de) 2019-12-01 2022-10-05 The Procter & Gamble Company Haarkonditionierungsmittel mit einem konservierungssystem, das natriumbenzoat und glykole und/oder glycerylester enthält
USD962050S1 (en) 2020-03-20 2022-08-30 The Procter And Gamble Company Primary package for a solid, single dose beauty care composition
USD941051S1 (en) 2020-03-20 2022-01-18 The Procter And Gamble Company Shower hanger
USD965440S1 (en) 2020-06-29 2022-10-04 The Procter And Gamble Company Package
CN116018123A (zh) 2020-08-11 2023-04-25 宝洁公司 含有芸苔油醇缬氨酸酯乙磺酸盐的保湿毛发调理剂组合物
MX2023001046A (es) 2020-08-11 2023-02-16 Procter & Gamble Composiciones acondicionadoras para el cabello de viscosidad baja que contienen esilato de valinato de brassicilo.
US11696882B2 (en) 2020-08-11 2023-07-11 The Procter & Gamble Company Clean rinse hair conditioner compositions containing brassicyl valinate esylate
EP4255384A1 (de) 2020-12-01 2023-10-11 The Procter & Gamble Company Wässrige haarkonditionierungszusammensetzungen mit gelösten antischuppenwirkstoffen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028107A1 (en) * 1993-06-02 1994-12-08 The Procter & Gamble Company Perfume delivery system comprising zeolites
WO1999027069A1 (en) * 1997-11-26 1999-06-03 The Procter & Gamble Company Detergent tablet
WO1999051715A1 (en) * 1998-04-06 1999-10-14 The Procter & Gamble Company Electrostatically coated non-particulate detergent product
DE19925518A1 (de) * 1999-06-04 2000-12-07 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit Parfüm
WO2002090481A1 (en) * 2001-05-04 2002-11-14 The Procter & Gamble Company Compositions and articles for effective deposition of perfume
US20030166489A1 (en) * 2001-12-20 2003-09-04 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Process for production of detergent tablets

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4539135A (en) * 1983-06-01 1985-09-03 Colgate Palmolive Co. Perfume-containing carrier for laundry compositions
JPH11512483A (ja) * 1995-09-18 1999-10-26 ザ、プロクター、エンド、ギャンブル、カンパニー ゼオライトを含有した高効率デリバリーシステム
US6245731B1 (en) * 1997-09-01 2001-06-12 The Procter & Gamble Company Detergent tablets-package combination
US6399564B1 (en) * 1997-11-26 2002-06-04 The Procter & Gamble Company Detergent tablet
US6498135B1 (en) * 1998-04-06 2002-12-24 Procter & Gamble Company Process for producing electrostatically coated non-particulate detergent product
AU5371399A (en) * 1998-07-29 2000-02-21 Benckiser N.V. Composition for use in a washing machine
EP1201741A1 (de) * 2000-10-31 2002-05-02 The Procter & Gamble Company Waschmittelzusammensetzungen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028107A1 (en) * 1993-06-02 1994-12-08 The Procter & Gamble Company Perfume delivery system comprising zeolites
WO1999027069A1 (en) * 1997-11-26 1999-06-03 The Procter & Gamble Company Detergent tablet
WO1999051715A1 (en) * 1998-04-06 1999-10-14 The Procter & Gamble Company Electrostatically coated non-particulate detergent product
DE19925518A1 (de) * 1999-06-04 2000-12-07 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit Parfüm
WO2002090481A1 (en) * 2001-05-04 2002-11-14 The Procter & Gamble Company Compositions and articles for effective deposition of perfume
US20030166489A1 (en) * 2001-12-20 2003-09-04 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Process for production of detergent tablets

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2355776B1 (de) * 2008-12-08 2017-11-15 The Procter and Gamble Company Poröses und lösliches feststoffsubstrat sowie oberflächenhaftende anorganische partikelparfumkomplexe
US11944693B2 (en) 2010-07-02 2024-04-02 The Procter & Gamble Company Method for delivering an active agent
US11970789B2 (en) 2010-07-02 2024-04-30 The Procter & Gamble Company Filaments comprising an active agent nonwoven webs and methods for making same
US11944696B2 (en) 2010-07-02 2024-04-02 The Procter & Gamble Company Detergent product and method for making same
CN105199887B (zh) * 2015-10-19 2018-10-02 茗燕生物科技(上海)有限公司 速溶型柚皮提取物洗衣片及其制作方法
CN105199887A (zh) * 2015-10-19 2015-12-30 茗燕生物科技(上海)有限公司 速溶型柚皮提取物洗衣片及其制作方法
US9816056B2 (en) 2015-10-19 2017-11-14 The Procter & Gamble Company Associating a scent with a laundry article
WO2017069933A1 (en) * 2015-10-19 2017-04-27 The Procter & Gamble Company Process for associating a scent with a laundry article
US11529292B2 (en) 2017-01-27 2022-12-20 The Procter & Gamble Company Compositions in the form of dissolvable solid structures
US11951194B2 (en) 2017-01-27 2024-04-09 The Procter & Gamble Company Compositions in the form of dissolvable solid structures comprising effervescent agglomerated particles
US11666514B2 (en) 2018-09-21 2023-06-06 The Procter & Gamble Company Fibrous structures containing polymer matrix particles with perfume ingredients
US11679066B2 (en) 2019-06-28 2023-06-20 The Procter & Gamble Company Dissolvable solid fibrous articles containing anionic surfactants
US11597191B2 (en) 2019-10-14 2023-03-07 The Procter & Gamble Company Biodegradable and/or home compostable sachet containing a solid article
US11525104B2 (en) 2019-11-20 2022-12-13 The Procter & Gamble Company Porous dissolvable solid structure
US11925698B2 (en) 2020-07-31 2024-03-12 The Procter & Gamble Company Water-soluble fibrous pouch containing prills for hair care
US11826439B2 (en) 2020-09-10 2023-11-28 The Procter & Gamble Company Dissolvable solid article containing anti-bacterial actives
US12029799B2 (en) 2022-04-27 2024-07-09 The Procter & Gamble Company Conditioning hair care compositions in the form of dissolvable solid structures

Also Published As

Publication number Publication date
JP2007525590A (ja) 2007-09-06
CA2558206A1 (en) 2005-09-22
US20050202992A1 (en) 2005-09-15
BRPI0508538A (pt) 2007-08-14
WO2005087906A1 (en) 2005-09-22

Similar Documents

Publication Publication Date Title
EP1574561A1 (de) Parfümierte Waschmitteltablette
KR100466468B1 (ko) 부가제, 특히 방향제 같은 세제 부가제로 충전된 캡슐화된다공성 담체를 갖는 전달 시스템
JP3308546B2 (ja) 複数の表面被覆を有する洗濯用添加剤粒子
US6790814B1 (en) Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
EP0701600B1 (de) Zeolithhaltiges parfümfreisetzungssystem
CA2282405C (en) Laundry additive particle having multiple surface coatings
US20030045446A1 (en) Delivery system having encapsulated porous carrier loaded with additives
JP2000503708A (ja) 改良された物理的性質を有する香料の送出のための粒状ランドリー添加剤組成物の製造用二重被覆方法
EP1517983B1 (de) Riechstoffzusammensetzung
WO2005005591A1 (en) Fabric freshener compositions
WO1998054283A1 (de) Waschmittelformkörper mit verbesserten auflöseeigenschaften
WO2002090481A1 (en) Compositions and articles for effective deposition of perfume
JP2002513075A (ja) 水に容易に分散する非粒状洗剤製品の製法
EP1820844A1 (de) Bleichefreie Waschmitteltablette
MXPA06010248A (en) Perfumed detergent tablets
DE19843938A1 (de) Wasch- und Reinigungsmittelformkörper mit grobteiligen Aufbereitungskomponenten
DE10065711A1 (de) Duftstoff-Zubereitung
MXPA99008579A (en) Laundry additive particle having multiple surface coatings
MXPA98008663A (en) Laundry additive particle having multiple surface coatings

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17P Request for examination filed

Effective date: 20060330

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20081029

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20101001